The present invention relates to a novel process for the preparation of hydroxyapatite.
Many different kinds of inorganic minerals are used in oral hygiene as cleaning substances for the production of toothpastes for cleaning the teeth. To mention only a few examples, those which can be used are dicalcium phosphate, calcium carbonate, silica, Maddrell's salt, alumina and others. Of these cleaning substances, not all are noncontroversial in view of their chemical and ionic composition.
Important factors for the suitability of a material as a tooth-cleaning substance in a toothpaste are a defined hardness of the substance, a very fine and closely defined grain structure, and a specific surface constitution and/or degree of roughness and absorptiveness to water/glycerol mixtures.
The abrasiveness of tooth-cleaning substances is determined by various processes (cf. F. J. Dany: Seifen Ole, Fette, Wachse, 104 (1978), pp. 306-310). The abrasiveness of the materials according to the invention was determined by the copper plate method, but there are certain correlations between the analytical methods. To achieve a very narrow and reproducible abrasiveness, three product parameters are essential. Attention must be paid to a specific grain structure (degree of fineness), a specific surface structure on the crystal/agglomerate and a high crystallinity.
The human teeth consist largely, and in particular the outer dental enamel, of calcium phosphates or more exactly of calcium hydroxyapatite of high purity. It is therefore natural to use precipitated calcium hydroxyapatite as a cleaning substance which has a substantial identity with the natural dental enamel.
Many methods for the precipitation of hydroxyapatite are known from the literature (CA, B 1142-55). In these processes, hydroxyapatite precipitates in very finely crystalline form in nearly all solutions. The crystals tend to agglomerate in solution and during the subsequent isolation of the solid. It thus appears that only very different and hardly reproducible materials can be produced in the conventional ways by metering a calcium source--such as calcium hydroxide, milk of lime or calcium carbonate--into a dilute phosphoric acid or into a dilute alkali metal phosphate solution or conversely a phosphate/phosphoric acid solution into a milk of lime, also under closely controlled precipitation parameters from the point of view of a defined abrasiveness. It ensues from this that in all precipitation processes of industrial importance, dicalcium phosphate is coprecipitated as a by-product and cannot be removed from the final product. This material exhibits different crystal hardnesses and is therefore completely undesirable in the material according to the invention.
It is known from U.S. Pat. No. 4,274,879, for example, to prepare hydroxyapatite by mixing milk of lime with at least 60% phosphoric acid in stoichiometric amounts at temperatures of 80.degree.-85.degree. C. and a pH of the reaction solution of about 9.0-11.0 in a continuous reaction. The products obtained are approximately spherical crystals having a diameter of 0.03 .mu.m to 0.5 .mu.m and a hydroxyapatite content of 98.5-99.5%. They are suitable for preparing bone replacement parts by sintering at temperatures of 700.degree. C. They are unsuitable as tooth-cleaning substances on account of their fineness.
It is known from U.S. Pat. No. 4,324,772 to mix, in a two-stage process, first milk of lime and phosphoric acid at 70.degree.-85.degree. C. and at a pH of 9.5-11, preferably at 10.5, in order to prevent formation of dicalcium phosphate impurities due to the excess of calcium hydroxide, and then to lower the pH to 7.0-7.4 in a second stage by addition of further phosphoric acid in order to neutralize excess calcium hydroxide. A hydroxyapatite having a grain size of less than 1 .mu.m results which, if the process is not carried out exactly, contains slight impurities of included Ca(OH).sub.2. This product is unsuitable as a tooth-cleaning substance.
A further process for the preparation of hydroxyapatite is known from U.S. Pat. No. 4,849,193, in which an acidic premixture of phosphoric acid and calcium hydroxide solution is first prepared which has the approximate composition of a monocalcium phosphate and a pH of 1.5-3.5, preferably 2.0. This is slowly metered at 23.degree. C. into a container of calcium hydroxide, a pH of over 12 being maintained, which only falls to 11-11.5 on addition of all the phosphoric acid. A finely divided hydroxyapatite is obtained which, after sintering at 1000.degree. C., has a grain size of 0.2 .mu.m and according to X-ray analysis is free of other calcium phosphates. This material is unsuitable as a tooth-cleaning substance.